Process to prepare crosslinked cellulose ethers, crosslinked cellulose ethers obtainable by such process and the use thereof

ABSTRACT

The invention relates to a dry or slurry process to prepare phosphate-crosslinked cellulose ethers from a cellulose starting material comprising the steps of adding an alkalizing agent to the cellulose starting material to achieve mercerization, adding an ethehfying agent to the reaction mixture to achieve etherification of the cellulose, and adding a crosslinking agent to the reaction mixture to achieve crosslinking of the cellulose, wherein at least part of the alkalizing agent is added to the cellulose starting material before the etherification and/or crosslinking reactions take place to obtain alkalized cellulose; the crosslinking agent and the etherifying agent are added one after the other in random order or simultaneously; the crosslinking agent is an alkali metal thmetaphosphate; and the crosslinking and etherification steps are performed at an elevated temperature. Additionally, the invention relates to crosslinked cellulose ethers obtainable by the above process having a viscosity and/or water absorption capacity higher than their non-crosslinked equivalents and the use thereof.

REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. patent application Ser. No.12/937,813, filed on Oct. 14, 2010, which is a national stage filingunder 35 U.S.C. § 371 of PCT/EP2009/054348, filed Apr. 10, 2009, whichclaims priority to European Patent Application No. 08154474.4, filedApr. 14, 2008, and U.S. Provisional Patent Application No. 61/046,116,filed on Apr. 18, 2008, the contents of which are each incorporatedherein by reference in their entirety.

The present invention relates to a process to preparephosphate-crosslinked cellulose ethers, to phosphate-crosslinkedcellulose ethers obtainable by such a process, and the use thereof.

JP 51028185 discloses a process to prepare a phosphate-crosslinkedcarboxymethyl cellulose (CMC) by adding to CMC 5-30% of sodiumhexametaphosphate (SHMP), blending the mixture, and heating to atemperature between 100 and 160° C. In all examples the crude (orintermediate) CMCs were purified in one way or another to obtainmaterials with a neutral or acidic pH before crosslinking. The productsmade are said to be ion exchange materials with low swelling power,which materials are generally not soluble in aqueous systems andconsequently do not contribute to any viscosity enhancement. Besides,clearly such products do not have a high water absorption capacity whenthey have low swelling capacity.

As the preparation of cellulose ethers takes place at an alkaline pH, itwould be much less laborious to start the crosslinking step with anon-purified alkaline cellulose ether, omitting the intermediate step ofadjusting the pH as required by the process disclosed in JP 51028185. Itmight also be advantageous to carry out the crosslinking step underalkaline conditions prior to or simultaneously with the etherificationstep.

WO 2005/123781 discloses a process to prepare a water-absorbingpolysaccharide, comprising the steps of contacting an uncrosslinkedpolysaccharide such as carboxymethyl cellulose (CMC) or hydroxyethylcellulose (HEC) with a polyphosphate or polyphosphoric acid as thecrosslinking agent in the presence of water while forming apolysaccharide gel, and subsequently crosslinking said polysaccharidegel. The crosslinking reaction is performed under alkaline conditionsand at a temperature of 70-300° C. The thus obtained polysaccharide gelis subsequently dried, resulting in a polymer preferably containing nomore than 10 wt % of water that can be ground to give a powder.

The process disclosed in WO 2005/123781 is disadvantageous because itrequires the formation of a gel before the crosslinking step isperformed, which gel subsequently needs to be dried again, making thisprocess difficult to incorporate into a common cellulose etherificationprocess. The crosslinked products obtained by the process disclosed inthis application are characterized by a slimyness of 1, which impliesthat after wetting of the crosslinked cellulose the particles form a gelin which the separate particles are still recognizable.

In P. K. Chatterjee, B. S. Gupta, eds., Textile Science and TechnologyVol. 13, Absorbent Technology (Elsevier 2002), Chapter VII entitled“Crosslinked Cellulose and Cellulose Derivatives”, an overview ofcrosslinking agents for cellulose derivatives is provided. Manycrosslinking agents are mentioned, including phosphorous oxychloride,which is an undesired chemical from a health and safety point of view.

The purpose of the present invention is to provide a process to preparephosphate-crosslinked cellulose ethers that can be operated at arelatively low temperature while reducing the number of steps, and as aconsequence is more (energy) efficient. Additionally, a purpose of theinvention is to provide a process in which a non-hazardous (green)crosslinking agent can be used. Another purpose of the invention is toprovide crosslinked cellulose ethers that have a higher viscosity thantheir non-crosslinked equivalents and are soluble in an aqueoussolution.

It has now been found that the drawbacks of the state of the art can beremoved and the above purpose achieved by a dry or slurry process toprepare phosphate-crosslinked cellulose ethers from a cellulose startingmaterial comprising the steps of adding an alkalizing agent to thecellulose starting material to achieve mercerization, adding anetherifying agent to the reaction mixture to achieve etherification ofthe cellulose, and adding a crosslinking agent to the reaction mixtureto achieve crosslinking of the cellulose, wherein

-   -   at least part of the alkalizing agent is added to the cellulose        starting material before the etherification and/or crosslinking        reactions take place to obtain alkalized cellulose;    -   the crosslinking agent and the etherifying agent are added one        after the other in random order or simultaneously;    -   the crosslinking agent is an alkali metal trimetaphosphate; and    -   the crosslinking and etherification steps are performed at an        elevated temperature.

It is understood that in the above process more alkalization andetherification steps can be performed. In one embodiment, etherificationsteps may be performed with different etherifying agents, or with amixture containing more than one etherifying agent, resulting in acellulose ether containing different substituents.

In a preferred embodiment the crosslinking agent and the etherifyingagent are added to the reaction mixture when it has an alkaline pH.Alternatively, though less preferred, the crosslinking agent and/or theetherifying agent may already have been added to the cellulose startingmaterial before the alkaline agent is added. In such an embodiment theetherification and crosslinking reactions will not start before theaddition of the alkaline agent.

A dry or slurry process means a process wherein the reaction mediumconsists of dry flocs, which are dry or wetted solid particles (flocs)which are—in general—relatively free-flowing, or consists of a slurry,which slurry encompasses solid particles suspended (and/or dispersed) ina fluid reaction medium.

The reaction may be conducted in a relatively large amount of diluent orwith a minimal amount of diluent as desired, i.e. giving the so-calledslurry and the so-called dry process, respectively.

In this specification, the term slurry process stands for a processwhere the weight ratio of liquid medium to cellulose is greater than 10,while a dry process means a process where the weight ratio of liquidmedium to cellulose is equal to or smaller than 10, preferably smallerthan 5, more preferably smaller than 3. Typically, a dry process iscarried out in a high-efficiency intensive mixer, e.g. a plowsharemixer.

The terms dry and slurry are used to specifically exclude a processwherein the reaction medium is a gel. A gel can be defined as acolloidal system which is soft and jelly-like, which is mostly liquid incomposition but has the structural coherence of a solid.

It should be understood that reacting cellulose ethers with phosphatecompounds, like STMP, in a solution, especially a lowly concentratedsolution, does not lead to crosslinked cellulose ethers but tophosphorylated cellulose ethers instead, i.e. to cellulose ethers thatare substituted with phosphate groups.

Additionally, the invention provides phosphate-crosslinked celluloseethers obtainable by the above process, characterized in that they havea higher viscosity than their non-crosslinked equivalents when measuredin an aqueous solution, and the use thereof as thickeners, waterbinders, water retention agents, stabilizers, rheology modifying agents,as well as the use thereof in mining, building, in coatings, adhesives,oil drilling, and health care applications.

It has been found that when cellulose ethers are crosslinked, theviscosity of the products increases at first, but if the crosslinkingreaction continues, the viscosity decreases to below the level of thenon-crosslinked substituted equivalent cellulose compound. If thereaction is completed before the viscosity falls below the startingviscosity, a product is obtained that has a higher viscosity and isstill soluble in water.

In accordance with the invention the viscosity of the non-crosslinkedand crosslinked cellulose ethers is measured using a TA Instruments AR1000 Rheometer at 0.1 s⁻¹ using a 40 mm, 4° steel cone and plategeometry at 25° C. For the viscosity measurement a solution of thecellulose ether of 1, 1.5, 2, 3 or 4 wt % in water is taken. Theconcentration at which the viscosity of the crosslinked cellulose etheris determined is the concentration at which the non-crosslinkedequivalent has a viscosity of between about 1,000 and 5,000 mPas.

The phosphate-crosslinked cellulose ethers according to the inventionhaving a higher viscosity than their non-crosslinked equivalents aresoluble in water, which means that in general when wetted they firstform a gel and after the addition of further water they will dissolve.

In a preferred embodiment, the phosphate-crosslinked cellulose ethersobtainable by the process are crosslinked with 0.00001-0.75 mol % ofSTMP per anhydroglucose unit, preferably with 0.0001-0.5 mol % STMP peranhydroglucose unit.

Additionally, it has been found that when the cellulose ethers arecrosslinked, an initial increase in water absorption capacity occurs.Upon further crosslinking this water absorption capacity decreases toeven below the level of the non-crosslinked equivalent cellulose ether.Hence, slight crosslinking not only turns out to be a means to increasethe viscosity but also a means to increase the water absorption power ofthe cellulose ethers.

Additionally, the invention provides phosphate-crosslinked celluloseethers obtainable by the above process, characterized in that they havea higher water absorption capacity than their non-crosslinkedequivalents, and the use thereof as thickeners, water binders, waterretention agents, stabilizers, rheology modifying agents, as well as theuse thereof in mining, building, in coatings, adhesives, oil drilling,and health care applications.

It has surprisingly been found that in the process of the invention, thereaction under alkaline conditions with sodium trimetaphosphate (STMP)clearly gives cross-linked product of the cellulose ether, while SHMP(sodium hexametaphosphate) and STPP (sodium tripolyphosphate) providebarely any cross-linked product under the same reaction conditions.

The term “elevated temperature” used for the crosslinking andetherification steps of the process of the present invention means atemperature above 20° C., preferably of above 40° C., most preferably ofabove 60° C. The temperature in a preferred embodiment is below 100° C.,preferably below 95° C., and most preferably below 90° C.

The crosslinking step in the process is generally performed at atemperature of 40-120° C. In a preferred embodiment for the preparationof crosslinked CMC, the temperature is 50-80° C., even more preferably60-70° C.

The gel-free process of the invention can be performed at a reactiontemperature of 65° C., while some of the state of the art processesrequire a temperature of 100° C. or higher and, moreover, it was foundnot to be necessary to purify the reaction product as some state of theart processes require. In one embodiment, consequently, the crosslinkingstep of the process may immediately follow the etherification stepwithout any intermediate neutralization or acidification step whilemaintaining an alkaline pH, or may even take place overlapping orsimultaneously with the etherification step. Nor does the process of theinvention require the formation of a gel of the cellulose before thecrosslinking step can be performed, which makes the process much moreefficient as there is then no need to dry the gel again. Moreover, theprocess of the invention provides crosslinking on the cellulosebackbone, i.e. does not require carboxyalkyl groups for the crosslinksto be formed.

The cellulose product of the invention is preferably etherified with atleast one carboxyalkyl, alkyl and/or hydroxyalkyl substituent, morepreferably a carboxyalkyl and/or alkyl substituent having 1 to 6 carbonatoms, even more preferably 1-3 carbon atoms, and/or a hydroxyalkylsubstituent having 2-6 carbon atoms, even more preferably 2-3 carbonatoms. Also minor amounts of long chain alkyl substituents may bepresent, containing 6-24 carbon atoms, and quaternary ammoniumsubstituents. Even more preferably, the substituted cellulose iscarboxymethyl cellulose (CMC), hydroxyethyl cellylose (HEC),hydroxypropyl cellulose (HPC), methyl cellulose (MC), methylhydroxyethyl cellulose (MHEC), ethyl hydroxyethyl cellulose (EHEC),methylethyl hydroxyethyl cellulose (MEHEC), methyl hydroxypropylcellulose (MHPC) or a hydrophobically modified analogue thereof, mostpreferred are CMC, EHEC, and MEHEC.

The etherifying agents can be selected from the group of epoxyalkanes,halogenated alkanes, and halogenated carboxylic acids, but are notlimited thereto.

The fluids (diluents) used in the process to form the reaction mediummay be any solvent or liquid medium known to the person skilled in theart that provides a good mixing of the reactants and prevents smearingof the reactor content before or during etherification and crosslinking(i.e. does not lead to the formation of a gel). The composition of thefluid mixture may be changed during the process. For example, in theetherification and crosslinking steps different fluids can be present inthe reaction mixture.

Suitable diluents include alcohols, ketones, such as acetone, methylethyl ketone, ethers, water, or mixtures of two or more of thesediluents. In a preferred embodiment for the preparation of a crosslinkedcarboxyalkyl cellulose, the fluid may be an alcohol, more preferably aC1-C4 alcohol, like isopropyl alcohol or ethanol, or a mixture of analcohol and water. For the preparation of a crosslinked (hydroxyl)alkylcellulose the fluid may be an alcohol, an ether or one of theetherifying agents. One or more of the etherifying agents may also actas a diluent. In a preferred embodiment for the preparation of EHEC thefluid may be ethyl chloride.

The amount of liquid medium is such that the cellulose content ispreferably 5-70 wt % on total weight of liquid medium plus crosslinkedsubstituted cellulose.

The crosslinking agent and the etherifying agent can be added to thereaction mixture in the presence or absence of a fluid. The fluid shouldnot be chosen such that the reaction mixture will become a gel. It iswithin the skills of a person skilled in the art, using the abovedisclosure, to choose the right fluids.

The alkaline pH during the crosslinking step of the process is generallyhigher than 7, preferably higher than 8, more preferably higher than 9and preferably lower than 14, more preferably lower than 13, even morepreferably below 11.

The alkaline pH during the etherification step of the process isgenerally higher than 7, preferably higher than 9, more preferablyhigher than 10. Preferably, the pH is below 14.

It is known to a person skilled in the art that during an etherificationthe pH decreases. Therefore, in one embodiment it may be necessary toadd additional alkaline agent to keep the pH in the desired alkalinerange during the etherification.

It should be understood that the more alkaline the pH is during theetherification and crosslinking steps, the lower the elevatedtemperature may be. Indeed, as a person skilled in the art willacknowledge, one should not perform the reaction steps at both anextremely alkaline pH and an extremely high reaction temperature, asunder such circumstances the crosslink will become susceptible todegradation, which is undesirable.

It is understood that it is possible to purify the end products of theprocess of the invention. Suitable methods for purifying are known to aperson skilled in the art. Purification can for example be carried outby washing procedures, as they are known for cellulose ethers in thestate of the art. At a high crosslinking degree when the amount ofwater-insoluble cellulose ethers increases, washing can even be donewith cold water.

The invention is illustrated by the examples below, which are notlimiting for the invention

EXAMPLES

In the Examples the following test methods are employed:

The Settling Volume Measurement

1.5 grams of the dried (crosslinked) cellulose ether are thoroughlymixed with 100 ml water in a 100 ml measuring cylinder. After standingfor 4 hours a sediment may be formed, giving a certain settling volume,expressed in ml.

The settling volume is used as a measure for the crosslink density ofthe product. A settling volume of >90 ml in the above test indicatesthat the product contains no or few insolubles (no or only slightcrosslinking). A settling volume of <25 ml (for a purified material) or<35 ml (for a crude material) indicates a lot of sedimentation and is ameasure for a dense crosslink network.

Turbidity Measurement

The turbidity of a solution of (crosslinked) cellulose ether in waterwas measured using a Monitek® Model 251 turbidimeter (forward scatterdesign, Monitek GmbH). The turbidity value is related to the amount ofinsoluble material in a solution. Light crosslinking, which enhances theviscosity, will not give a remarkable increase in the amount ofinsoluble material and thus a lower value for turbidity. The turbiditywill however go up when the amount of crosslinks increases, which givesrise to considerable amounts of insoluble material.

Viscosity Measurement

The viscosity of a solution of (crosslinked) cellulose ether in waterwas measured with a TA Instruments AR 1000 Rheometer at 0.1 s⁻¹ using a40 mm, 4° steel cone and plate geometry. For the viscosity measurement asolution of the cellulose ether of 1, 1.5, 2, 3 or 4 wt % in water istaken. The concentration at which the viscosity of the crosslinkedcellulose product is determined is the concentration at which thenon-crosslinked equivalent cellulose ether has a viscosity of betweenabout 1,000 and 5,000 mPas.

Water Absorption Capacity

The water absorption capacity of the crosslinked cellulose ethers wasdetermined using a tea bag test. 50 mg (crosslinked) cellulose etherwere weighed into a sealable teabag of approx 7.5 cm×7.5 cm. After beingsealed the teabag was soaked in a container with water for 20 minutes.The teabag was removed from the container and drained for one minute ona paper towel. The weight of the tea bag with (crosslinked) celluloseether was determined before and after water absorption, as was theweight of a reference without (crosslinked) cellulose ether. The numberof grams of water absorbed per gram of (crosslinked) cellulose ether wascalculated.

The following materials were used

Sodium trimetaphosphate (STMP): Sigma T5508

Sodium tripolyphosphate (STPP): Acros Organics No. 218675000

Sodium hexametaphosphate (SHMP): Aldrich No. 305553

Cellulose was used from both a cotton linters and a wood source, asfurther specified below.

Example 1 Preparation of Crosslinked CMC in Ethanol

16.6 kg cellulose (cotton linters) were mixed with 10.0 kg ethanol and16.1 kg of a 50 wt % aqueous solution of caustic soda. After mixing for24 minutes, 1.22 kg of 75 wt % solution of monochloroacetic acid inethanol were added. The mixture was heated to 80° C. in about 30 minutesand after stirring for 50 minutes at this temperature the mixture wascooled to room temperature. The pH of a 2% solution in water was 11.5.

350 g of the crude reaction mixture, having a CMC content of about 42 wt%, were taken and 100 g ethanol/water (60/40 w/w) were added thereto. Tothis mixture were added 0.34 g sodium hydroxide in 10 ml water and 7.97g sodium trimetaphosphate (STMP) in 80 ml water (4 mole % relative tothe anhydroglucose units). The mixture was mixed for 30 minutes at roomtemperature, heated to 80° C. in 30 minutes, and mixed for another hourat 80° C. After cooling down the mixture was dried for 30 minutes at 65°C. in a fluid bed dryer. The resulting product was subjected to asettling volume test, giving a 30 ml settling volume.

Example 2 Preparation of Crosslinked CMC in Ethanol

116 g of the crude reaction mixture of Example 1, having a CMC contentof about 42 wt %, were suspended in 300 ml ethanol water (40/60 w/w).0.166 g of sodium trimetaphosphate (STMP) dissolved in 40 ml of waterwas added, corresponding to 0.25 mole % STMP relative to the amount ofanhydroglucose units of the CMC. The mixture was mixed for 2 hours atroom temperature, heated to 80° C. in about 45 minutes, and mixed for anadditional 15 minutes. After cooling down, 100 ml of ethanol were addedand the mixture was neutralized with acetic acid. The cellulose productwas filtered off and washed with ethanol/water (65/35 w/w), twice withethanol/water (80/20 w/w), and once with 96% ethanol. The purifiedproduct was dried in vacuum at 30° C., after which it was analyzed usingthe methods below. Using the above method, the viscosity was measured ina 1% solution in water. The turbidity of a 1 wt % solution in water wasmeasured using the above method.

Example 2 was repeated with different amounts of STMP which correspondto 0.00 (Comparative Example 2a), 0.05 (Example 2b), 0.50 (Example 2d),0.75 (Example 2e), and 1.00 (Example 2f) mole % STMP per anydroglucoseunit of the CMC.

The results are given in Table 1 below.

TABLE 1 Characteristics of the crosslinked cellulose ethers of Example 2Viscosity of Turbidity of STMP 1% solution 1% solution Example (mole %)STMP (gram) (mPas) (ppm) 2a 0.00 2840 57 (comparative) 2b 0.05 0.033n.d. 79 2c 0.25 0.166 5880 65 2d 0.50 0.332 12090 75 2e 0.75 0.497 4430496 2f 1.00 0.663 n.d. >1000 n.d. means not determined

It is demonstrated that using relatively low amounts of crosslinkingagent gives products that have a higher viscosity than theirnon-crosslinked equivalents. Also it is demonstrated that a higherdegree of crosslinking gives an increased turbidity, i.e. an increasedamount of insolubles.

Example 3 Preparation of Crosslinked CMC in Isopropyl Alcohol

687 g of cellulose (wood cellulose) were mixed with 906 g of isopropylalcohol and 701 g of an aqueous solution of 49 wt % of caustic soda.After mixing for 20 minutes 453 g of isopropyl alcohol and 473 g of a 80wt % solution of monochloro-acetic acid in water were added. The mixturewas heated to 80° C. in about 30 minutes and after stirring for 90minutes at this temperature the mixture was cooled down to 30° C. Anamount of 73 grams of sodium trimetaphosphate (6 mole % relative to theanhydroglucose units) in 654 ml of water was added to the reactionmixture. The mixture was heated to 65° C. in 30 minutes and kept at thistemperature for 30 minutes. The reaction mixture was cooled down to roomtemperature and dried in a fluid bed dryer for 30 minutes at 65° C.

The settling volume was determined using the above method. The settlingvolume was found to be 21 ml. The viscosity of a 2% solution of theproduct was measured using above method and found to be less than 100mPas.

Example 4 Preparation of Crosslinked CMC in Isopropyl Alcohol

The procedure of Example 3 was followed with the following deviations.

Before the addition of monochloroacetic acid, an amount of caustic sodawas added to the mixture as specified in Table 2 below.

The amount of STMP added was 0.00 (Comparative Example 4a), 0.50(Example 4b), 0.75 (Example 4c), 1.00 (Example 4d), 1.25 (Example 4e),and 3.00 (Example 4f) mole %, respectively, relative to theanhydroglucose units in the cellulosic starting material. The amountsare specified in Table 2 below.

TABLE 2 Caustic soda and STMP used in Example 4 Caustic soda STMP (mole% STMP (g in 650 ml Example (50 wt %) (g) re AGU) water) 4a(comparative) 675 0 0 4b 678 0.50 6.1 4c 679 0.75 9.2 4d 681 1.00 12.24e 683 1.25 15.3 4f 694 3.00 36.6

The viscosity and settling volume of the products obtained weredetermined. The viscosity was measured using a 2% solution of thenon-purified product using the above method. Additionally, the waterabsorption capacity of the crosslinked cellulose ethers was determinedusing the above tea bag test.

TABLE 3 Settling volume and viscosity of crosslinked cellulose etherproducts of Example 4 STMP Settling Viscosity Water (mole volume (2%solution) absorption Example % on AGU) (ml) (mPas) capacity (g/g) 4a0.00 >90 3907 30 (comparative) 4b 0.50 >90 28120 62 4c 0.75 >90 20890 524d 1.00 >90 10280 45 4e 1.25 >90 4033 39 4f 3.00 41 n.d. 23

It is demonstrated that using relatively low amounts of crosslinkingagent gives products that have a higher viscosity and water absorptioncapacity than their non-crosslinked equivalents.

Comparative Examples 5 and 6 Preparation of Crosslinked CMC Using otherPhosphate Crosslinking Agents

Example 3 was repeated with the following deviation. Instead of sodiumtrimeta-phosphate (STMP) an equivalent amount of sodium tripolyphosphate(STPP) was used (Comparative Example 5) or an equivalent amount ofsodium hexameta-phosphate (SHMP) was used (Comparative Example 6). Thesettling volume of the products obtained was measured. The viscosity wasalso measured for the product of Example 6 in a 2% solution using aBrookfield viscositymeter, type LVF, at 30 rpm and 25° C.

TABLE 4 Characteristics of crosslinked cellulose ether products ofComparative Examples 5 and 6 Comparative Amount of phosphate Settlingvolume Viscosity of 2% Example crosslinker (g) (ml) solution (mPas) 588 >90 6 76 >90 14,640

The high settling volumes show that these alternative crosslinkingagents give no or barely any crosslinks in a cellulose ether. Theviscosity increase measured for the product of Comparative Example 6compared to comparative Example 4a was found to be the result of a smalldegree of crosslinking having taken place when using SHMP.

Example 7 Preparation of Crosslinked CMC in Isopropyl Alcohol

687 g of cellulose (wood cellulose) were mixed with 906 g of isopropylalcohol and 714 g of an aqueous solution of 49 wt % of caustic soda.After mixing for 20 minutes, 453 g isopropyl alcohol, 473 g of 80 wt %solution of monochloroacetic acid in water, and 73 g of sodiumtrimetaphosphate in about 250 ml water were added. The mixture washeated to 80° C. in about 30 minutes and mixed for 90 minutes at thistemperature. The reaction mixture was cooled down to room temperatureand dried in a fluid bed dryer for 30 minutes at 65° C. The settlingvolume was found to be 80 ml.

Example 8 Preparation of Crosslinked EHEC

8 kg wood cellulose were mixed with 14 kg ethyl chloride and 6 kg of a50 wt % aqueous solution of caustic soda. After mixing 7 kg of ethyleneoxide were added in portions. The temperature was gradually increased to100° C. and the reactor content was mixed for an additional 25 minutes.After cooling down the excess ethyl chloride was evaporated.

50 g of the crude reaction mixture, having an EHEC content of about 55wt %, were taken and 0.8 g sodium hydroxide in 10 ml water were addedthereto. After mixing for 30 minutes 3.2 g sodium trimetaphosphate(STMP) in 20 ml water were added (10 mole % relative to the amount ofanhydroglucose units). The mixture was mixed for 60 minutes at 80° C.After cooling down the mixture was washed three times with 2 wt % sodiumsulfate solution at 95° C. The washed material was dried for 30 minutesat 70° C. in a fluid bed dryer. The resulting product was subjected to asettling volume test, giving a 21 ml settling volume. The viscosity of a1% solution of the product was measured using the above method and foundto be less than 120 mPas.

Example 9 Preparation of Crosslinked EHEC

50 g of the crude reaction mixture of Example 8, having an EHEC contentof about 55 wt %, were mixed with 0.16 g of sodium trimetaphosphate(STMP) dissolved in 20 ml of water, corresponding to 0.50 mole % STMPrelative to the amount of anhydroglucose units of the EHEC. The mixturewas mixed 1 hour at 80° C.

After cooling down the mixture was washed three times with 2 wt % sodiumsulfate solution at 92° C. The washed material was dried for 30 minutesat 70° C. in a fluid bed dryer.

Example 9 was repeated with different amounts of STMP which correspondto 0.00 (Comparative Example 9a) and 6.6 (Example 9c) mole % STMP peranhydro-glucose unit of the EHEC. In Example 9c an amount of 0.6 gram ofsodium hydroxide in 10 ml water was added before STMP addition asdescribed in Example 8.

Using the above method, the viscosity was measured in a 1% solution inwater. The results are given in Table 5 below.

TABLE 5 Characteristics of the crosslinked cellulose ethers of Example 9Viscosity of 1% Example STMP (mole %) STMP (gram) solution (mPas) A 0.000.00 1,155 (comparative) B 0.50 0.16 1,626 C 6.6 2.1 360

It is demonstrated that using relatively low amounts of crosslinkingagent gives products that have a higher viscosity than theirnon-crosslinked equivalents and that using relatively high amounts ofcrosslinking agent gives products with an even lower viscosity than thenon-crosslinked cellulose ether.

The invention claimed is:
 1. A dry or slurry process to preparephosphate-crosslinked cellulose ethers from a cellulose startingmaterial comprising the steps of adding an alkalizing agent to thecellulose starting material to achieve mercerization, adding anetherifying agent to the reaction mixture to achieve etherification ofthe cellulose, and adding a crosslinking agent to the reaction mixtureto achieve crosslinking of the cellulose, wherein at least part of thealkalizing agent is added to the cellulose starting material before theetherification and/or crosslinking reactions take place to obtainalkalized cellulose; the crosslinking agent and the etherifying agentare added one after the other in random order or simultaneously; thecrosslinking agent is an alkali metal trimetaphosphate; and thecrosslinking and etherification steps are performed at an elevatedtemperature of between 20 and 95° C.; wherein the crosslinking step iscarried out at an alkaline pH of higher than 7; and wherein the amountof crosslinking agent added to the reaction mixture is sufficiently highthat the phosphate-crosslinked cellulose ethers prepared by said dry orslurry process are insoluble in water.
 2. The process of claim 1 whereinthe crosslinking step is carried out subsequent to the etherificationstep.
 3. The process of claim 2 wherein the crosslinking step followsthe etherification step without an intermediate neutralization step. 4.The process of claim 3 wherein the process is a slurry process thattakes place in a reaction medium that is a liquid comprising water andan alcohol and the cellulose ether is a carboxyalkyl cellulose ether. 5.The process of claim 1 wherein the crosslinking step is carried out atan alkaline pH of higher than
 8. 6. The process of claim 3 wherein thealkali metal trimetaphosphate is sodium trimetaphosphate.
 7. The processof claim 2 wherein the process is a slurry process that takes place in areaction medium that is a liquid comprising water and an alcohol and thecellulose ether is a carboxyalkyl cellulose ether.
 8. The process ofclaim 2 wherein the alkali metal trimetaphosphate is sodiumtrimetaphosphate.
 9. The process of claim 1 wherein the process is aslurry process that takes place in a reaction medium that is a liquidcomprising water and an alcohol and the product of the etherificationstep is a carboxyalkyl cellulose ether.
 10. The process of claim 9wherein the carboxyalkyl cellulose ether is carboxymethyl celluloseether.
 11. The process of claim 9 wherein the alkali metaltrimetaphosphate is sodium trimetaphosphate.
 12. The process of claim 1wherein the alkali metal trimetaphosphate is sodium trimetaphosphate.